WO2023151532A1

WO2023151532A1 - Method for directly preparing chemicals from crude oil

Info

Publication number: WO2023151532A1
Application number: PCT/CN2023/074592
Authority: WO
Inventors: 吴青
Original assignee: 中国海洋石油集团有限公司; 中海油化工与新材料科学研究院(北京)有限公司
Priority date: 2022-02-08
Filing date: 2023-02-06
Publication date: 2023-08-17
Also published as: CN116606671A

Abstract

The present invention relates to the field of catalysis technology for oil refining and chemical engineering, and discloses a method for directly preparing chemicals from crude oil. The method comprises: (1) contacting crude oil with a DPC-1 catalyst for a first reaction to obtain a first reaction product containing a spent DPC-1 catalyst; (2) contacting the first reaction product and heavy cycle oil with a DPC-2 catalyst for a second reaction to obtain a second reaction product; (3) fractionating the second reaction product to obtain chemicals; and (4) circulating at least one of gasoline, diesel oil and wax oil to step (2) to serve as the heavy cycle oil, wherein the alkalinity of the DPC-1 catalyst is higher than that of the DPC-2 catalyst, and the DPC-2 catalyst contains an aluminosilicate type molecular sieve ZEO-1. The method provided in the present invention has a strong adaptability to raw materials, can be used for treating both high-quality crude oil and inferior crude oil and various types of heavy oil, and can improve the distribution of the chemicals, improve the yield and quality of the chemicals, and reduce the yield of coke.

Description

Method for directly producing chemicals from raw material oil

Cross References to Related Applications

This application claims the benefit of Chinese patent application 202210120892.3 filed on February 08, 2022, the contents of which are incorporated herein by reference.

technical field

The invention relates to the technical field of refining and chemical catalysis, in particular to a method for directly producing chemicals from raw material oil.

Background technique

The catalytic technology route of direct crude oil to chemicals refers to the method of directly converting crude oil into light olefins and aromatics under the action of catalysts to maximize the production of olefins and aromatics chemicals. Crude oil direct-to-chemicals technology can maximize the conversion of crude oil resources into basic organic chemical raw materials, and is an effective way to make full use of primary fossil resources such as crude oil; it can "skip" atmospheric and vacuum distillation and raw material refining in traditional oil refining The process can reduce equipment investment, resource waste, reduce processing energy consumption, and reduce greenhouse gas emissions.

India's Reliance Corporation has developed a multi-zone catalytic cracking (MCC) process for direct cracking of crude oil without the use of atmospheric and vacuum devices, and can also be used in combination with the cracking of condensate oil, shale oil and tight oil. Sinopec Research Institute of Petrochemical Sciences proposed two methods of directly producing chemicals from crude oil, one of which is used to process paraffin-based high-quality light crude oil: first cut paraffin-based high-quality light crude oil into light and heavy fractions, Then in a double riser reactor Catalytic cracking of light fractions and heavy fractions to maximize the production of light olefins; one is used to treat naphthenic intermediate base crude oil: first hydrotreating naphthenic intermediate base crude oil, and then performing catalytic cracking.

Other research units, such as China University of Petroleum (East China) and the Institute of Process Research, Chinese Academy of Sciences, have also conducted research on the direct production of chemicals from crude oil, but they all use high-quality light paraffinic base crude oil as raw materials, and consider dividing the raw materials into light and heavy fractions to enter them separately. For the method of catalytic cracking with two risers, the technologies of the above-mentioned companies also emphasize the need for harsh conditions such as very high reaction temperature (such as 670-730° C.), very high agent-to-oil ratio (such as 25 or more). Tsinghua University emphasized its down-bed reactor technology, which has the advantage of increasing propylene production compared with traditional catalytic cracking technology.

However, the current crude oil direct-to-chemicals technology route generally has poor adaptability to raw materials, and generally can only be used to process high-quality raw materials, such as paraffin-based light crude oil, and cannot be directly used to process non-paraffin-based inferior raw materials. Even if high-quality feedstock oil is used to dilute or hydrotreat low-quality feedstock oil, it is difficult to obtain high-yield and high-quality chemicals.

Therefore, there is an urgent need to provide a method for directly producing chemicals from raw material oil with strong adaptability to raw materials, which can improve the distribution of chemicals and increase the yield of chemicals.

Contents of the invention

The purpose of the present invention is to provide a method for directly producing chemicals from crude oil to solve the problems of poor raw material adaptability, poor chemical distribution, low yield and high coke yield in the prior art.

In order to achieve the above object, the invention provides a method for directly producing chemicals from raw material oil method, the method includes the following steps:

(1) contacting the raw material oil with the DPC-1 catalyst for the first reaction to obtain the first reaction product containing the DPC-1 catalyst to be produced;

(2) contacting the first reaction product containing the DPC-1 catalyst to be produced, the recycled oil and the DPC-2 catalyst for a second reaction to obtain a second reaction product;

(3) fractionating the second reaction product to obtain chemicals;

(4) At least one of gasoline, diesel oil and wax oil in the chemicals is recycled to step (2) as the back refining oil;

Wherein, the basicity of the DPC-1 catalyst is stronger than that of the DPC-2 catalyst, and the DPC-2 catalyst contains aluminosilicate molecular sieve ZEO-1.

Through the above technical scheme, the beneficial technical effects obtained by the present invention are as follows:

1) A method for directly producing chemicals from feedstock oil provided by the invention, first utilizes DPC-1 catalyst to react first with feedstock oil, then mixes the first reaction product containing DPC-1 catalyst to be produced with recycled oil and containing The DPC-2 catalyst of the aluminosilicate molecular sieve ZEO-1 is contacted for the second reaction, and the DPC-1 catalyst and the DPC-2 catalyst work together, which not only improves the adaptability of the method of directly producing chemicals from raw material oil to raw materials, It can be used not only to process high-quality crude oil, but also to process low-quality crude oil and various types of heavy oil. At the same time, it can further reduce the yield of wax oil and coke, and further increase the content of low-carbon olefins in the obtained chemicals, especially dry The content of ethylene in the gas; for example, when using the method of the present invention to process the intermediate-naphthenic feedstock oil, the dry gas yield is between 2.2-3wt%, and the content of ethylene in the dry gas is ≥50%;

2) a kind of raw material oil method that the present invention directly manufactures chemicals does not need to first The reaction product is subjected to the separation operation of the catalyst and the reaction product, the process flow is simple, the investment is low, and the method is suitable for industrial promotion.

Detailed ways

Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.

In the present invention, the basicity of the catalyst can be tested on a Quantachrome ChemBet 3000 chemisorption instrument by temperature programmed carbon dioxide adsorption (CO ₂ -TPD). A 150 mg catalyst sample was pretreated at 600 °C for 1 h under a He gas atmosphere, and then cooled to 100 °C for _CO2 adsorption. Use CO ₂ /He mixed gas with a volume ratio of 1:9 as the adsorption gas, adsorb at 100°C for 30 min, and then purge with He gas for 30 min to remove physically adsorbed CO ₂ . Finally, desorption was performed at a rate of 16°C min ^-1 under He atmosphere, and the desorption temperature was increased from 100°C to 600°C to obtain a CO ₂ -TPD spectrum. Read the CO ₂ desorption peak temperature from the CO ₂ -TPD spectrum, and calculate the number of alkali centers at the CO ₂ desorption peak position. Among them, the higher the _CO2 desorption peak temperature, the more the number of alkali centers at the _CO2 desorption peak position, and the stronger the alkalinity of the catalyst.

The invention provides a method for directly producing chemicals from raw material oil, the method comprising the following steps:

(1) The first reaction occurs when the raw oil is contacted with the DPC-1 catalyst to obtain the The first reaction product of raw DPC-1 catalyst;

(3) fractionating the second reaction product to obtain chemicals;

In step (1):

Among them, in the present invention, the first reaction that occurs when the feedstock oil contacts the DPC-1 catalyst includes cracking "shearing" reactions and refining reactions, which are used to remove sulfur, nitrogen, metals, carbon residues and other substances in the feedstock oil, In order to improve the catalytic cracking effect of subsequent feedstock oil, improve the distribution of chemicals, and improve the yield and quality of chemicals.

In a preferred embodiment, the raw oil is selected from crude oil and/or heavy oil; wherein, the crude oil refers to unrefined petroleum produced, and the heavy oil refers to crude oil processed to extract light components The remaining residue can be selected from straight-run wax oil, coker wax oil, hydrogenated wax oil, atmospheric residue, vacuum residue, etc. Distillate oil.

In the present invention, the method for directly producing chemicals from raw material oil provided by the present invention has strong raw material adaptability and does not need to make special restrictions on crude oil. Specifically, when divided by the basic properties of crude oil, crude oil can be divided into paraffinic base crude oil, intermediate base crude oil, intermediate-naphthenic crude oil and naphthenic crude oil. The method for directly producing chemicals from raw material oil provided by the present invention , both available For the treatment of paraffinic crude oil, it can also be used for the treatment of intermediate base crude oil, intermediate-naphthenic crude oil and naphthenic crude oil. When divided according to the density of crude oil, crude oil can be divided into light crude oil, medium crude oil, heavy crude oil and extra thick crude oil. The method for directly producing chemicals from raw material oil provided by the present invention can be used to treat light Crude oil and medium crude oil can also be used to process heavy crude oil and extra viscous crude oil such as oil sand bitumen and Venezuelan extra heavy oil. The raw oil in the present invention can be a single crude oil, or a single heavy oil, or multiple crude oils, multiple heavy oils, or a mixed oil of crude oil and heavy oil. That is, the raw oil is selected from one or more of oil sand bitumen, Venezuelan extra heavy oil, straight-run gas oil, coker gas oil, hydrogenated gas oil, atmospheric residue, and vacuum residue.

In a preferred embodiment, the DPC-1 catalyst includes 85-99 parts by weight of carrier I and 1-15 parts by weight of active metal oxide I; wherein, the carrier I is selected from alumina, silicon oxide, At least one of titanium oxide and zirconium oxide; the active metal oxide I is selected from alkali metal oxides and/or alkaline earth metal oxides.

In a preferred embodiment, the DPC-1 catalyst includes 90-98 parts by weight, preferably 94-97 parts by weight of carrier I and 2-10 parts by weight, preferably 3-6 parts by weight of active metal oxide I.

In a preferred embodiment, the carrier I is selected from alumina and/or silica, preferably silica.

In a preferred embodiment, the active metal oxide I is at least one selected from calcium oxide, magnesium oxide, barium oxide, and strontium oxide, preferably magnesium oxide and/or barium oxide.

In a preferred embodiment, the _CO2 desorption peak temperature of the DPC-1 catalyst is 185-195°C, preferably 187-192°C; the number of alkali centers at the _CO2 desorption peak position is 16-22 mmol/g, preferably 18-21 mmol/g.

In a preferred embodiment, the bulk ratio of the DPC-1 catalyst is 0.5-0.65 g/mL, preferably 0.55-0.6 g/mL; the average particle size is 30-110 μm, preferably 40-80 μm.

In a preferred embodiment, the reaction conditions of the first reaction include: the mass ratio of the DPC-1 catalyst to the feedstock oil is 5-20:1, preferably 8-15:1.

In a preferred embodiment, the reaction conditions of the first reaction further include: the temperature of the first reaction is 380-550°C, preferably 410-535°C; the pressure of the first reaction is 0.1-1MPa, preferably 0.1 -0.4MPa; the time of the first reaction is 0.1-4s, preferably 0.5-3s.

In step (2):

In a preferred embodiment, the recycled oil is selected from at least one of gasoline, diesel oil and wax oil in the chemicals, preferably wax oil.

Wherein, in the present invention, the second reaction is carried out under the joint action of the DPC-1 catalyst and the DPC-2 catalyst, and the wax oil is used as the refining oil, which can further improve the output of low-carbon olefins in the second reaction product, and reduce the wax oil and coke. yield.

In a preferred embodiment, the DPC-2 catalyst includes 75-95 parts by weight of carrier II, 3.5-8 parts by weight of active metal oxide II and 5-20 parts by weight of aluminosilicate molecular sieve ZEO- 1; wherein, the carrier II is selected from at least one of alumina, silicon oxide, titanium oxide, and zirconia; the active metal oxide II is selected from alkali metal oxides and/or alkaline earth metal oxides.

In a preferred embodiment, the DPC-2 catalyst preferably includes 80-90 parts by weight of carrier II, 4-5 parts by weight of active metal oxide II and 10-15 parts by weight of aluminosilicate molecular sieve ZEO -1.

In a preferred embodiment, the carrier II is selected from alumina and/or silica, preferably silica.

In a preferred embodiment, the active metal oxide II is at least one selected from calcium oxide, magnesium oxide, barium oxide, and strontium oxide, preferably calcium oxide and/or magnesium oxide.

In a preferred embodiment, the carrier I and the metal active component I in the DPC-1 catalyst are the same as the carrier II and the metal active component II in the DPC-2 catalyst.

In a preferred embodiment, the aluminosilicate molecular sieve ZEO-1 is an aluminosilicate molecular sieve with a multi-dimensional ultra-large pore structure, and its synthesis method includes using tricyclohexylmethylphosphonium (tCyMp) It is an organic template agent, aluminum hydroxide is the aluminum source, and ethyl orthosilicate is the silicon source, and it is synthesized under hydrothermal conditions. Among them, the inventors of the present invention have found through research that introducing aluminosilicate molecular sieve ZEO-1 into the DPC-2 catalyst can increase the content of low-carbon olefins in the obtained second reaction product.

In a preferred embodiment, the _CO2 desorption peak temperature of the DPC-2 catalyst is 165-184°C, preferably 169-182°C; the number of alkali centers at the _CO2 desorption peak position is 2-13mmol/g, Preferably it is 3-11 mmol/g.

In a preferred embodiment, the heap ratio of the DPC-2 catalyst is at least 0.2 g/mL larger than the heap ratio of the DPC-1 catalyst, preferably 0.75-0.9 g/mL; The difference between the particle size and the average particle size of the DPC-1 catalyst is at least ≥ 20 μm, preferably the difference is 20-40 μm.

In a preferred embodiment, the mass ratio of the DPC-2 catalyst to the raw oil is 5-20:1, preferably 7-13:1; the mass ratio of the recycled oil to the raw oil is The amount ratio (that is, the refining ratio) is 0.1-0.5:1, preferably 0.2-0.4:1.

In a preferred embodiment, the DPC-2 catalyst is carried by the first reaction product in contact with the recycled oil.

In a preferred embodiment, the reaction conditions of the second reaction further include: the reaction temperature of the second reaction is 495-515°C, preferably 500-510°C; the pressure of the second reaction is 0.1-1MPa, It is preferably 0.1-0.4 MPa; the second reaction time is at least 1.5s longer than the first reaction time, preferably 2-3s longer.

In a preferred embodiment, the first reaction and the second reaction are carried out in a riser reactor; wherein, the riser reactor includes a first reaction zone, a second reaction zone and a settler, and the pre-lift Under the action of a medium, the feedstock oil and the DPC-1 catalyst are contacted in the first reaction zone to undergo the first reaction to obtain a first reaction product containing the raw DPC-1 catalyst; the raw DPC-1 catalyst containing The first reaction product and back-refined oil and DPC-2 catalyst enter the second reaction zone, and the second reaction occurs in contact with the second reaction zone, and the raw DPC-1 catalyst containing the raw DPC-1 and the raw DPC-2 catalyst are obtained. 2. The mixture of the catalyst and the second reaction product; the mixture is contacted with stripping steam in the settler for stripping, and the second reaction product is separated from the raw DPC-1 catalyst and the raw DPC-2 catalyst to obtain the first two reaction products.

In a preferred embodiment, the pre-lift medium is at least one selected from water vapor, dry gas, natural gas and liquefied gas, preferably water vapor.

In a preferred embodiment, the mass ratio of the raw material oil to the pre-lift medium is 100:1-10, preferably 100:1-5.

In a preferred embodiment, the stripping steam is selected from steam, dry gas, natural At least one of natural gas and liquefied gas, preferably water vapor.

In a preferred embodiment, the mass ratio of the feedstock oil to the stripping steam is 100:1-8, preferably 100:2-5.

In a preferred embodiment, the spent DPC-1 catalyst and spent DPC-2 catalyst are analyzed, and the coke yield is 3-7%, preferably 4.5-6%.

In step (3):

In a preferred embodiment, the present invention does not specifically limit the fractionation operation of the second reaction product, and can perform fractionation according to the conventional fractionation operation in the art according to the specific distribution of chemicals in the second reaction product, and the present invention no longer to repeat.

In a preferred embodiment, the chemicals include dry gas, liquefied gas, gasoline, diesel and wax oil. Among them, the distillation range of gasoline is 35-200°C, the distillation range of diesel oil is 200-380°C, and the wax oil is distillate oil above 380°C.

In a preferred embodiment, the yield of the dry gas is 0.3-6%, preferably 0.6-4.5%; the yield of the liquefied gas is 15-50%, preferably 22-40%; the The yield of gasoline is 25-47%, preferably 28-40%; the yield of the diesel oil is 12-32%, preferably 15-26%; the yield of the wax oil is 5-20%, preferably 4-18%.

In a preferred embodiment, in the dry gas, the content of ethylene is ≥50wt%, preferably 55-70wt%, more preferably 60-65wt%. Among them, the method for directly preparing chemicals from raw material oil provided in the present invention uses a DPC-2 catalyst containing aluminosilicate molecular sieve ZEO-1 to catalyze the second reaction, which can increase the content of ethylene in the dry gas to more than 50 wt%. , can maximize the added value of dry gas.

In a preferred embodiment, in the liquefied gas, carbon triolefins and carbon tetraolefins The total amount of content is 60-98wt%, preferably 70-95wt%; in the gasoline, the content of olefins above _C5 is 30-60wt%, preferably 40-55wt%.

In a preferred embodiment, the content of aromatics in the diesel is 70-95wt%, preferably 75-90wt%.

The method for directly producing chemicals from raw material oil provided by the invention has strong raw material adaptability, can be used not only for processing light crude oil, but also for processing heavy crude oil and heavy oil, and can further reduce the yield of wax oil and improve the obtained chemical The content of dry gas and liquefied petroleum gas in the product is suitable for industrial promotion.

The present invention will be described in detail below by way of examples. Wherein, the DPC-1 catalyst used in the embodiment contains 95wt% of silicon oxide and 5wt% of magnesia, and the _CO2 desorption peak temperature of the DPC-1 catalyst is 189 ° C, and the alkali center of the _CO2 desorption peak position The quantity is 20.27mmol/g, the heap ratio is 0.55g/mL, and the average particle size is 60μm;

DPC-2 catalyst contains 80wt% silicon oxide, 2.5wt% calcium oxide, 2.5wt% magnesium oxide and 15wt% aluminosilicate type molecular sieve ZEO-1; CO desorption peak temperature of DPC- ₂ catalyst It is 172°C, the number of alkali centers at the _CO2 desorption peak position is 8.85mmol/g, the heap ratio is 0.85g/mL, and the average particle size is 80μm.

Wherein, the preparation method of silicate type molecular sieve ZEO-1 in DPC-2 catalyst comprises:

(1) Synthesis of organic mechanism-directing agent OSDA: 24.6g of Tricyclohexylphosphine (Tricyclohexylphosphine) was added to 250mL of acetonitrile, and 48.20g of methyl iodide (MeI) was added dropwise under ice bath conditions, and stirred at room temperature after the addition was completed 2 days, remove solvent with rotary evaporator, obtain 36.30g tricyclohexylmethylphosphine iodide (TCyMP);

Add 24.10g TCyMP iodide to the mixture of 200mL water and 200mL anion exchange resin (type: Dowex Monosphere 550A; exchange capacity: 1.2mmol/mL wet resin), filter after stirring for 12h, collect the OSDAOH solution; Concentrate to obtain the organic organization directing agent OSDA;

(2) Synthesis of silicate-type molecular sieve ZEO-1: Add 43.61mg of Al(OH) ₃ (the water content of Al(OH) ₃ is 14.4wt%) to 49.04g of OSDA with a concentration of 0.1935mmol/g, and stir The mixture was added until all Al(OH) ₃ was completely hydrolyzed, then 3.984g Si(OEt) ₄ was added, stirring was continued for 12h, and then transferred to an oven at 85°C for drying to remove excess water to obtain a gel. Then the gel was transferred to an autoclave, and crystallized at 200°C for 20 days, followed by filtration, washing and drying, and then calcined at 600°C for 6 hours to obtain ZEO-1 molecular sieve.

The intermediate-naphthenic marine heavy crude oil PL19-3 and the intermediate-based atmospheric residue in the examples all come from CNOOC Huizhou Petrochemical Co., Ltd.

Example 1

(1) Under the action of pre-lifting steam (water vapor), the DPC-1 catalyst and the intermediate-naphthenic marine heavy crude oil PL19-3 are countercurrently contacted in the first reaction zone of the riser reactor to undergo the first reaction. The temperature of the first reaction is 480°C, the pressure of the first reaction is 0.23MPa, and the time of the first reaction is 2s, and the first reaction product containing the to-be-born DPC-1 catalyst is obtained; wherein, the DPC-1 catalyst and the intermediate-naphthene The mass ratio of base marine heavy crude oil PL19-3 is 8:1, and the mass ratio of intermediate-naphthenic marine heavy crude oil PL19-3 to pre-lifting medium is 100:3.3;

(2) The above-mentioned first reaction product is loaded with DPC-2 catalyst and enters the second reaction zone of the riser reactor, and the second reaction occurs in countercurrent contact with the recycled oil in the second reaction zone, and the temperature of the second reaction is 505 ° C. The pressure of the second reaction is 0.22MPa, and the time of the second reaction is 4s to obtain a mixture containing the DPC-1 catalyst to be born, the DPC-2 catalyst to be born and the second reaction product; The ratio is 0.3, and the mass ratio of DPC-2 catalyst to intermediate-naphthenic marine heavy crude oil PL19-3 is 10:1;

The above mixture is contacted with stripping steam (steam) in a settler for stripping, and the second reaction product is separated from the unused DPC-1 catalyst and the unused DPC-2 catalyst to obtain the second reaction product; wherein, the intermediate - The mass ratio of naphthenic marine heavy crude oil PL19-3 to stripping steam is 100:5;

Analyzing the isolated DPC-1 catalyst and DPC-2 catalyst, the coke yield was 5.2%;

(3) The above-mentioned second reaction product is fractionated to obtain dry gas with an ethylene content of 61.1wt%, a liquefied gas with a total content of carbon triolefins and carbon tetraolefins of 95.2wt%, and a content of olefins above _C5 of 52.2 wt% gasoline, diesel oil with an aromatic content of 80wt%, and wax oil; wherein, the yield of dry gas is 2.3%, the yield of liquefied gas is 28.3%, the yield of gasoline is 32.3%, and the yield of diesel oil is 23.4%, the yield of wax oil is 8.5%;

(4) The wax oil obtained by fractional distillation is recycled to step (2) as back refining oil.

Example 2

(1) Under the action of pre-lifting steam (steam), the DPC-1 catalyst and the intermediate base atmospheric residue are countercurrently contacted in the first reaction zone of the riser reactor to undergo the first reaction. The temperature of the first reaction is 520°C, the pressure of the first reaction is 0.27MPa, and the time of the first reaction is 2.5s, and the first reaction product containing the unborn DPC-1 catalyst is obtained; wherein, the DPC-1 catalyst and the intermediate base are usually The mass ratio of pressure residue oil is 15:1, and the mass ratio of intermediate base atmospheric residue oil to pre-lifting medium is 100:4.5;

(2) The above-mentioned first reaction product is loaded with DPC-2 catalyst and enters the second reaction zone of the riser reactor, and the second reaction occurs in countercurrent contact with the recycled oil in the second reaction zone. The temperature of the second reaction is 515 ° C, The pressure of the second reaction is 0.26MPa, and the time of the second reaction is 5s to obtain a mixture containing the DPC-1 catalyst to be born, the DPC-2 catalyst to be born and the second reaction product; The ratio is 0.35, and the mass ratio of DPC-2 catalyst to intermediate base atmospheric residue is 10:2;

The above mixture is contacted with stripping steam (steam) in a settler for stripping, and the second reaction product is separated from the unused DPC-1 catalyst and the unused DPC-2 catalyst to obtain the second reaction product; wherein, the intermediate The mass ratio of base atmospheric residue to stripping steam is 100:5;

The separated raw DPC-1 catalyst and the raw DPC-2 catalyst were analyzed, and the yield of coke obtained was 5.5wt%;

(3) The above-mentioned second reaction product is carried out fractional distillation, obtains the dry gas that ethylene content is 55.5wt%, and the content total amount of carbon three olefins and carbon four olefins is the liquefied gas of 96.1wt%, and the content of olefins above _C5 is 53.0 wt% gasoline, diesel oil with an aromatic content of 81.0wt%, and wax oil; among them, the yield of dry gas is 2.8%, the yield of liquefied gas is 23.4%, the yield of gasoline is 36.2%, and the yield of diesel oil For 27.2%, the yield of wax oil is 4.9%;

Comparative example 1

Identical with embodiment 1, difference is: contain the silicon oxide of 67wt% in the DPC-2 catalyst, the calcium oxide of 0.5wt%, the magnesium oxide of 1.0wt%, the ZSM-5 molecular sieve of 26.0wt% (silicon oxide/alumina The molar ratio is 30:1), 2.0wt% ZSM-48 molecular sieve (the molar ratio of silica/alumina is 100:1) and 3.5wt% Y-type molecular sieve (the molar ratio of silica/alumina is 5:1 ); the CO ₂ desorption peak temperature of the DPC-2 catalyst is 172 °C, the number of alkali centers at the CO ₂ desorption peak position is 8.85 mmol/g, the bulk ratio is 0.75 g/mL, and the particle size is 50 μm.

Among them, the yield of dry gas with an ethylene content of 42.3 wt% is 2.1%, the yield of liquefied gas with a total content of carbon triolefins and carbon tetraolefins of 91.5 wt% is 25.5%, and the content of olefins above _C5 is The yield of 45.7wt% gasoline was 32.9%, the yield of diesel oil with 77.2wt% aromatic content was 25.4%, the yield of wax oil was 9.3%, and the yield of coke was 4.8%.

The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.

Claims

A method for directly producing chemicals from raw material oil, characterized in that the method comprises the following steps:

(1) contacting the raw material oil with the DPC-1 catalyst for the first reaction to obtain the first reaction product containing the DPC-1 catalyst to be produced;

(2) contacting the first reaction product containing the DPC-1 catalyst to be produced, the recycled oil and the DPC-2 catalyst for a second reaction to obtain a second reaction product;

(3) fractionating the second reaction product to obtain chemicals;

(4) At least one of gasoline, diesel oil and wax oil in the chemicals is recycled to step (2) as the back refining oil;

Wherein, the basicity of the DPC-1 catalyst is stronger than that of the DPC-2 catalyst, and the DPC-2 catalyst contains aluminosilicate molecular sieve ZEO-1.
The method according to claim 1, wherein the raw oil is selected from crude oil and/or heavy oil;

Preferably, the crude oil includes light crude oil, medium crude oil, heavy crude oil and extra thick crude oil; the heavy oil is selected from straight-run gas oil, coker gas oil, hydrogenated gas oil, atmospheric residue, vacuum residue one or more of oils;

Preferably, the raw oil is selected from one or more of oil sand bitumen, Venezuelan extra heavy oil, straight-run gas oil, coker gas oil, hydrogenated gas oil, atmospheric residue, and vacuum residue.
The method according to claim 1 or 2, wherein the DPC-1 catalyst comprises 85-99 parts by weight of carrier I and 1-15 parts by weight of active metal oxide I; wherein, the carrier I is selected from At least one of aluminum, silicon oxide, titanium oxide, zirconium oxide; the active metal oxide I is selected from alkali metal oxides and/or alkaline earth metal oxides;

Preferably, the carrier I is selected from alumina and/or silicon oxide, more preferably silicon oxide;

Preferably, the active metal oxide I is at least one selected from calcium oxide, magnesium oxide, barium oxide, and strontium oxide, more preferably magnesium oxide and/or barium oxide;

Preferably, the CO2 desorption peak temperature of the DPC-1 catalyst is 185-195°C, preferably 187-192°C; the number of alkali centers at the CO2 desorption peak position is 16-22mmol/g, preferably 18- 21mmol/g;

Preferably, the bulk ratio of the DPC-1 catalyst is 0.5-0.65 g/mL, preferably 0.55-0.6 g/mL; the average particle size is 30-110 μm, preferably 40-80 μm.
The method according to any one of claims 1-3, wherein the reaction conditions of the first reaction include: the mass ratio of the DPC-1 catalyst to the feedstock oil is 5-20:1, preferably 8-15:1;

Preferably, the reaction conditions of the first reaction include: the temperature of the first reaction is 380-550°C, preferably 410-535°C; the pressure of the first reaction is 0.1-1MPa, preferably 0.1-0.4MPa; The reaction time is 0.1-4s, preferably 0.5-3s.
The method according to any one of claims 1-4, wherein the DPC-2 The catalyst includes 75-95 parts by weight of carrier II, 3.5-8 parts by weight of active metal oxide II and 5-20 parts by weight of aluminosilicate molecular sieve ZEO-1; wherein, the carrier II is selected from alumina, At least one of silicon oxide, titanium oxide, and zirconium oxide; the active metal oxide II is selected from alkali metal oxides and/or alkaline earth metal oxides;

Preferably, the carrier II is selected from alumina and/or silica, preferably silica;

Preferably, the active metal oxide II is at least one selected from calcium oxide, magnesium oxide, barium oxide, and strontium oxide, preferably calcium oxide and/or magnesium oxide;

Preferably, the CO2 desorption peak temperature of the DPC-2 catalyst is 165-184 °C, preferably 169-182 °C; the number of alkali centers at the CO2 desorption peak position is 2-13 mmol/g, preferably 3- 11mmol/g;

Preferably, the heap ratio of the DPC-2 catalyst is at least 0.2g/mL larger than the heap ratio of the DPC-1 catalyst, preferably 0.75-0.9g/mL; the particle size of the DPC-2 catalyst is the same as that of the DPC -1 The particle size difference of the catalyst is at least ≥ 20 μm, preferably the difference is 20-40 μm.
The method according to any one of claims 1-5, wherein the mass ratio of the DPC-2 catalyst to the feedstock oil is 5-20:1, preferably 7-13:1; The mass ratio to the raw material oil is 0.1-0.5:1, preferably 0.2-0.4:1;

Preferably, the reaction conditions of the second reaction further include: contacting the DPC-2 catalyst with the recycled oil under the support of the first reaction product;

Preferably, the reaction temperature of the second reaction is 495-515°C, preferably 500-510°C; the pressure of the second reaction is 0.1-1MPa, preferably 0.1-0.4MPa; the second reaction time is longer than the first A reaction time is at least 1.5s longer, preferably 2-3s longer.
The method according to any one of claims 1-6, wherein the first reaction and the second reaction are carried out in a riser reactor; wherein the riser reactor comprises a first reaction zone, a second In the reaction zone and the settler, under the action of the pre-lifting medium, the feedstock oil and the DPC-1 catalyst are contacted in the first reaction zone to undergo the first reaction, and the first reaction product containing the unused DPC-1 catalyst is obtained; The first reaction product containing the raw DPC-1 catalyst enters the second reaction zone with the recycled oil and the DPC-2 catalyst, and the second reaction occurs in contact with the raw DPC-1 catalyst in the second reaction zone to obtain the raw DPC-1 containing DPC-1 catalyst, the mixture of raw DPC-2 catalyst and the second reaction product; the mixture is contacted with stripping steam in the settler for stripping, and the second reaction product is mixed with the raw DPC-1 catalyst and the second reaction product The DPC-2 catalyst is separated to obtain a second reaction product.
The method according to claim 7, wherein the pre-lift medium is selected from at least one of water vapor, dry gas, natural gas, and liquefied gas, preferably water vapor;

Preferably, the mass ratio of the raw material oil to the pre-lift medium is 100:1-10, preferably 100:1-5.
The method according to claim 7 or 8, wherein the stripping steam is selected from at least one of water vapor, dry gas, natural gas, and liquefied gas, preferably water vapor;

Preferably, the mass ratio of the feedstock oil to the stripping steam is 100:1-8, preferably 100:2-5.
The method according to any one of claims 1-9, wherein the chemicals include dry gas, liquefied gas, gasoline, diesel oil and wax oil.